Polycycloolefin polymer and inorganic nanoparticle compositions as optical materials

1. A composition comprising:

a) one or more monomers of formula (I):

wherein:

m is an integer 0, 1 or 2;

R 1 , R 2 , R 3 and R 4 are the same or different and each independently selected from the group consisting of hydrogen, halogen, methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, hydroxy(C 1 -C 16 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 12 )bicycloalkyl, (C 7 -C 14 )tricycloalkyl, (C 6 -C 10 )aryl, (C 6 -C 10 )aryl(C 1 -C 6 )alkyl, perfluoro(C 6 -C 10 )aryl, perfluoro(C 6 -C 10 )aryl(C 1 -C 3 )alkyl, tri(C 1 -C 6 )alkoxysilyl and a group of formula (A):

—Z-Aryl  (A)

wherein:

Z is a bond or a group selected from the group consisting of:

(CR 5 R 6 ) a , O(CR 5 R 6 ) a , (CR 5 R 6 ) a O, (CR 5 R 6 ) a —O—(CR 5 R 6 ) b , (CR 5 R 6 ) a —O—(SiR 5 R 6 ) b , (CR 5 R 6 ) a —(CO)O—(CR 5 R 6 ) b , (CR 5 R 6 ) a —O(CO)—(CR 5 R 6 ) b , (CR 5 R 6 ) a —(CO)—(CR 5 R 6 ) b , where a and b are integers which may be the same or different and each independently is 1 to 12;

R 5 and R 6 are the same or different and each independently selected from the group consisting of hydrogen, methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, acetoxy, (C 2 -C 6 )acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C 3 -C 6 )alkyl, phenyl and phenoxy;

Aryl is phenyl or phenyl substituted with one or more of groups selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 6 )alkyl, hydroxy, methoxy, ethoxy, linear or branched (C 3 -C 6 )alkyloxy, acetoxy, (C 2 -C 6 )acyl, hydroxymethyl, hydroxyethyl, linear or branched hydroxy(C 3 -C 6 )alkyl, phenyl and phenoxy;

b) a latent organo-ruthenium compound selected from the group consisting of a compound of formula (IIIA) and a compound of formula (IIIC):

and

wherein:

X is selected from the group consisting of chlorine and iodine;

Y is O;

L is PR 3 , where R is independently selected from the group consisting of isopropyl, sec-butyl, tert-butyl, cyclohexyl, bicyclo(C 5 -C 10 )alkyl, phenyl, benzyl, isopropoxy, sec-butoxy, tert-butoxy, cyclohexyloxy, phenoxy and benzyloxy;

each R 8 is independently selected from the group consisting of methyl, ethyl, linear or branched (C 1 -C 6 )alkyl, (C 6 -C 10 )aryl, methoxy, ethoxy, linear or branched (C 1 -C 6 )alkoxy, (C 6 -C 10 )aryloxy, —NHCO(C 1 -C 6 )alkyl, —NHCO-perfluoro(C 1 -C 6 )alkyl, —SO 2 N((C 1 -C 6 )alkyl) 2 and —NO 2 ;

Ar 3 and Ar 4 are the same or different and each independently selected from the groan consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;

wherein said substituents are selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl and phenyl; and

c) one or more additives selected from the group consisting of a photoactive acid generator, a photoactive base generator, a thermal acid generator, a thermal base generator and a mixture in any combination thereof; and wherein

said monomer of formula (I) is having a refractive index of at least 1.5 and said composition is in a clear liquid form at room temperature.

2. The composition according to claim 1 , wherein said composition comprises first and second monomer of formula (I) distinct from each other and one of said first and second monomers having a refractive index of at least 1.5 and viscosity below 100 centipoise, and wherein said first monomer is completely miscible with said second monomer to form a clear solution.

3. The composition according to claim 1 , wherein said composition forms a substantially transparent film when heated to a temperature from 50° C. to 100° C.

4. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 90 percent of the visible light.

5. The composition according to claim 3 , wherein said film has a transmission of equal to or higher than 95 percent of the visible light.

6. The composition according to claim 1 , wherein the monomer of formula (I) is selected from the group consisting of:

5-(4-phenylbutyl)bicyclo[2.2.1]hept-2-ene;

5-(3-phenylpropyl)bicyclo[2.2.1]hept-2-ene;

5-phenethylbicyclo[2.2.1]hept-2-ene (PENB);

5-(benzyloxy)bicyclo[2.2.1]hept-2-ene;

5-octylbicyclo[2.2.1]hept-2-ene (OctNB);

5-decylbicyclo[2.2.1]hept-2-ene (DecNB);

4,4′-(bicyclo[2.2.1]hept-5-en-2-ylmethylene)bis(2,6-di-tert-butylphenol) (AOAONB);

bicyclo[2.2.1]hept-5-en-2-ylmethyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate (AONB);

5-norbornenylmethyleugenyl acetate (EuAcNB);

5-norbornenylmethyleugenol (EuOHNB);

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(methyl)diphenylsilane (NBCH 2 OSiMePh 2 );

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)diphenylsilane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)(ethyl)(methyl)(phenyl)silane;

(bicyclo[2.2.1]hept-5-en-2-ylmethoxy)dimethyl(phenyl)silane;

bicyclo[2.2.1]hept-5-en-2-yltrimethoxysilane (TMSNB);

bicyclo[2.2.1]hept-5-en-2-yltriethoxysilane (NBSi(OC 2 H 5 ) 3 );

bicyclo[2.2.1]hept-5-en-2-yl(tert-butoxy)dimethoxysilane;

(2-(bicyclo[2.2.1]hept-5-en-2-yl)ethyl)trimethoxysilane;

NB(NMeOH) 2 ; and

PhAcNB.

7. The composition according to claim 1 , wherein the organo-ruthenium compound is selected from the group consisting of:

1,3-bis(2,4,6-trimethyiphenylimidazolidin-2-ylidene)(tricyclohexylphosphine)-(2-oxobenzylidene)ruthenium(V) chloride;

where X=halogen, —OR a , —O(CO)R a , —OSO 2 R a , where R a is (C 1 -C 12 )alkyl, (C 3 -C 12 )cycloalkyl, (C 6 -C 14 )aryl;

where X is Cl or I and R 10 is hydrogen, NO 2 or Cl; and

8. The composition according to claim 1 , wherein one or more additive is selected from the group consisting of:

methyl 4-(1-methyl)octahydropyrrolo[1,2-a]pyrimidine benzoate, commercially available as CGI 1293;

1-(1-phenylethyl)octahydropyrrolo[1,2-a]pyrimidine, commercially available as CGI 90;

and (4-thiophenyl)phenyl-diphenylsulfonium hexafluorophosphate;

bis-(triphenylsulfonium) sulfide bis-hexafluorophosphate (collectively TS-HFP);

tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanesulfonate (TTBPS-PFBS);

tris(4-tert-butylphenyl)sulfonium triflate (TTBPS-TF);

triphenylsulfonium chloride (TSP-Cl);

(4-phenoxyphenyl)diphenylsulfonium triflate (PPDP-ST);

bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate (BTBI-PFBS);

bis(4-tert-butylphenyl)iodonium p-toluenesulfonate (BTBI-PTS);

bis(4-tert-butylphenyl)iodonium triflate (BTBPI-TF);

tolylcumyliodonium-tetrakis pentafluorophenylborate, commercially available as Rhodorsil 2074P;

diphenyliodonium chloride (DPI-Cl);

diphenyleneiodonium chloride (DPEI-Cl);

N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate (HNPCI-PFBS);

wherein R 11 , R 12 , R 13 and R 14 are the same or different and each independently selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 6 -C 10 )aryl, substituted or unsubstituted (C 6 -C 10 )aryl(C 3 -C 16 )alkyl, (C 3 -C 12 )cycloalkyl or wherein any two of R 11 , R 12 , R 13 and R 14 taken together with the nitrogen atom to which they are attached form a (C 3 -C 12 )cyclic or (C 5 -C 12 )bicyclic ring; and

R 15 is selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 6 -C 10 )aryl and substituted or unsubstituted (C 6 -C 10 )aryl(C 3 -C 16 )alkyl; and

wherein n is an integer from 0 to 5;

R 15 is as defined above;

R 16 selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 6 -C 10 )aryl and substituted or unsubstituted (C 6 -C 10 )aryl(C 3 -C 16 )alkyl; and

R 17 is independently selected from the group consisting of methyl, ethyl, linear or branched (C 3 -C 16 )alkyl, perfluoro(C 1 -C 12 )alkyl, substituted or unsubstituted (C 6 -C 10 )aryl and substituted or unsubstituted (C 6 -C 10 )aryl(C 3 -C 16 )alkyl.

9. A film comprising the composition of claim 1 .